EP0035753B1 - Procédé de préparation d'alcènes-1,1-dichlorés - Google Patents

Procédé de préparation d'alcènes-1,1-dichlorés Download PDF

Info

Publication number
EP0035753B1
EP0035753B1 EP81101575A EP81101575A EP0035753B1 EP 0035753 B1 EP0035753 B1 EP 0035753B1 EP 81101575 A EP81101575 A EP 81101575A EP 81101575 A EP81101575 A EP 81101575A EP 0035753 B1 EP0035753 B1 EP 0035753B1
Authority
EP
European Patent Office
Prior art keywords
formula
alkyl
radical
optionally
radicals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81101575A
Other languages
German (de)
English (en)
Other versions
EP0035753A3 (en
EP0035753A2 (fr
Inventor
Hans-Jochem Dr. Riebel
Fritz Dr. Maurer
Uwe Dr. Priesnitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to AT81101575T priority Critical patent/ATE3853T1/de
Publication of EP0035753A2 publication Critical patent/EP0035753A2/fr
Publication of EP0035753A3 publication Critical patent/EP0035753A3/de
Application granted granted Critical
Publication of EP0035753B1 publication Critical patent/EP0035753B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/19—Halogenated dienes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/2635—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving a phosphorus compound, e.g. Wittig synthesis

Definitions

  • the invention relates to a new process for the preparation of 1,1-dichloroalkenes.
  • 1,1-dichloroalkenes are obtained if lithium salts of dichloromethanephosphonic esters are reacted with aldehydes or ketones (see Synthesis 1975, 458-461 and 535-536).
  • the production of the lithium salts of dichloromethanephosphonic esters is complex. They are obtained from chloromethanephosphonic acid esters or trichloromethanephosphonic acid esters by reaction with butyllithium and optionally carbon tetrachloride at -70 to -80 ° C., using carefully dried solvents and requiring an inert gas atmosphere.
  • the a-hydroxy-phosphonic acid esters of the formula (IV) are obtained by reducing the oxo compounds of the formula (V) with sodium tetrahydridoborate, optionally using a diluent, such as, for. B. water or aqueous methanol, at temperatures between - 20 and + 50 ° C and maintaining the pH. between 5 and 8 by adding a buffering agent, such as. B. Sodium hydrogen phosphate (see Chem. Ber. 103 (1970), 2984-2986).
  • a water-immiscible solvent such as, for. B. methylene chloride, dries the extracts, filtered and distilled off the solvent under reduced pressure.
  • the corresponding aldehydes of the formula (IIa) can be prepared from the a-hydroxyphosphonic acid esters of the formula (IV) by treatment with sodium hydroxide solution at temperatures between 0 and 100 ° C., preferably between 10 and 50 ° C. (compare Chem. Ber. 103 (1970), 2984-2986).
  • aldehydes of the formula (Ila) are also obtained by reacting acid chlorides of the formula (VI) with lithium tritert.-butoxy-hydrido-aluminate, which has optionally been prepared in situ from lithium tetrahydridoaluminate and tert-butanol, optionally in the presence of a diluent, such as, for. B. tetrahydrofuran, at temperatures between - 100 and + 100 ° C, preferably between - 80 and + 50 ° C.
  • a diluent such as, for. B. tetrahydrofuran
  • diluents Practically all inert organic solvents, in particular aprotic polar solvents, are suitable as such. These include ethers such as. B. glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran and dioxane, carboxamides, such as. B. dimethylformamide, dimethylacetamide and N-methylpyrrolidone, sulfoxides such. B. dimethyl sulfoxide, phosphoric acid amides, such as. B. Hexamethylphosphorklaretriamid, and nitriles, such as. B. acetonitrile and propionitrile.
  • ethers such as. B. glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran and dioxane
  • carboxamides such as. B. dimethylformamide, dimethylacetamide and N-methylpyrrolidone
  • sulfoxides such as. B. dimethyl sul
  • the reaction temperature can be varied within a wide range. Generally one works between 0 and 150 ° C, preferably at 10 to 100 ° C.
  • the process according to the invention is generally carried out at normal pressure.
  • the starting materials of the formulas (11) and (111) are preferably initially introduced and the phosphorous triamide is added dropwise. The reaction mixture is stirred until the reaction is complete and then filtered.
  • the workup can be carried out by customary methods, for example by diluting the filtrate with water, with a water-immiscible organic solvent, such as. B. methylene chloride, extracted, the organic phase dries, filtered and evaporated.
  • a water-immiscible organic solvent such as. B. methylene chloride
  • the products remaining in the residue can be processed in the usual way, e.g. B. be cleaned by vacuum distillation.
  • the 1,1-dichloroalkenes to be prepared by the process according to the invention can in part be used as intermediates for the preparation of pyrethroids which have an insecticidal and acaricidal action (cf. DE-OS 2 326 077).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (1)

  1. Procédé de fabrication de 1,1-dichloroalcènes de formule I
    Figure imgb0019
    dans laquelle
    R' représente de l'hydrogène, un alcoyle en Ci-C5 éventuellement halogéno-substitué, un benzyle ou phényléthyle éventuellement halogéno-substitué ou un phényle éventuellement substitué par de l'halogène, alcoyle en C1-C4, alcoxy en C1-C4, méthylènedioxy, cyano et/ou nitro, et
    R2 représente un alcoyle en C1-C5 éventuellement halogéno-substitué, alcényle en C2-C5, alcinyle en C2-C5, benzyle ou phényléthyle éventuellement halogéno-substitué, phényle éventuellement substitué par de l'halogène, alcoyle en C1-C4, alcoxy en C1-C4, méthylènedioxy, cyano et/ou nitro, un styryle éventuellement halogéno-substitué ou le radical
    Figure imgb0020
    dans lequel Z représente un acétyle, cyano, carbamoyle, alcoxy (C1-C4) carbonyle ou COOM, M représentant de l'hydrogène, un métal alcalin, un équivalent de métal alcalino-terreux ou un radical ammonium, caractérisé en ce qu'on fait réagir des composés carbonylés de formule II
    Figure imgb0021
    dans laquelle R1 et R2 ont la signification indiquée plus haut, avec des esters d'acide trichlorométhane- phosphonique de formule III
    Figure imgb0022
    dans laquelle les R3 représentent individuellement un alcoyle ou phényle ou les deux radicaux R3 représentent ensemble un alcanediyle (alcoylène), en présence d'au moins la quantité équimolaire d'une triamide d'acide phosphoreux de formule IV
    Figure imgb0023
    dans laquelle les R4 représentent un alcoyle ou les deux radicaux R4 représentent ensemble un alcanediyle (alcoylène), et éventuellement en présence d'un diluant à des températures entre 0 et 150 °C.
EP81101575A 1980-03-12 1981-03-05 Procédé de préparation d'alcènes-1,1-dichlorés Expired EP0035753B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81101575T ATE3853T1 (de) 1980-03-12 1981-03-05 Verfahren zur herstellung von 1,1-dichloralkenen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3009486 1980-03-12
DE19803009486 DE3009486A1 (de) 1980-03-12 1980-03-12 Verfahren zur herstellung von 1,1-dichlor-alkenen

Publications (3)

Publication Number Publication Date
EP0035753A2 EP0035753A2 (fr) 1981-09-16
EP0035753A3 EP0035753A3 (en) 1981-11-18
EP0035753B1 true EP0035753B1 (fr) 1983-06-22

Family

ID=6096991

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81101575A Expired EP0035753B1 (fr) 1980-03-12 1981-03-05 Procédé de préparation d'alcènes-1,1-dichlorés

Country Status (8)

Country Link
US (1) US4350824A (fr)
EP (1) EP0035753B1 (fr)
JP (1) JPS56140937A (fr)
AT (1) ATE3853T1 (fr)
BR (1) BR8101423A (fr)
DE (2) DE3009486A1 (fr)
DK (1) DK111881A (fr)
IL (1) IL62322A0 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109852797B (zh) * 2017-12-16 2020-12-29 虔东稀土集团股份有限公司 一种用于萃取分离锂元素的萃取溶剂及其萃取分离锂元素的方法
CN111233618B (zh) * 2020-01-19 2022-06-07 浙江新和成股份有限公司 一种利用光气制备氯乙烯类化合物的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1127659A (fr) * 1977-12-16 1982-07-13 Pieter A. Verbrugge Procede d'obtention de composes de di-(halo)-vinyle
EP0048001B1 (fr) * 1980-09-12 1984-12-19 Farmos Group Ltd. Procédé de préparation de l'acide N-(4-(((2,4-diamino-6-ptéridinyl)méthyl)méthylamino)benzoyl)-glutamique

Also Published As

Publication number Publication date
EP0035753A3 (en) 1981-11-18
IL62322A0 (en) 1981-05-20
DE3160455D1 (en) 1983-07-28
BR8101423A (pt) 1981-09-15
DE3009486A1 (de) 1981-09-17
DK111881A (da) 1981-09-13
US4350824A (en) 1982-09-21
JPS56140937A (en) 1981-11-04
ATE3853T1 (de) 1983-07-15
EP0035753A2 (fr) 1981-09-16

Similar Documents

Publication Publication Date Title
EP0463464B1 (fr) Procédé pour la préparation de 2-chloro-5-méthylpyridine
EP0035753B1 (fr) Procédé de préparation d'alcènes-1,1-dichlorés
EP0035724B1 (fr) Procédé pour la préparation d'alcènes-1,1-dihalogénés
DE2643474C2 (de) Verfahren zur Herstellung von Phosphitchloriden
EP0023598B1 (fr) Procédé de préparation de 1,1-dichloroalcènes
EP0024611B1 (fr) Procédé de préparation de benzaldéhydes substitués
EP0035754B1 (fr) Procédé de préparation d'alcènes-1,1-dichlorés
DE2129583C3 (de) Verfahren zur Herstellung von Phosphinsäureanhydriden
EP0019719B1 (fr) Procédé de préparation d'alcènes, nouveaux intermédiaires pour leur préparation et procédé de les préparer
DE4020053A1 (de) Verfahren zur herstellung von 2-chlor-5-methyl-pyridin
EP0022971B1 (fr) Procédé pour la préparation de dérivés de l'acide 3-(2,2-dichlorovinyl)-2,2-diméthyl-cyclopropane-1-carboxylique
EP0024018B1 (fr) Procédé de préparation d'esters de l'acide alpha-oxo-alpha-(3-alcoxycarbonyl-2,2-diméthyl-cycloprop-1-yl) méthane phosphorique et leurs produits intermédiaires et procédé pour leur préparation
DE69907759T2 (de) Verbesserte regioselektive synthese von phosphonigsäuren
EP0031915B1 (fr) Procédé pour la préparation d'halogénoalcènes
EP0022984B1 (fr) Procédé de préparation de dérivés d'acide 3-(2.2-dichloro-vinyl)-2.2-diméthyl-cyclopropane-1-carboxylique
EP0270041B1 (fr) Procédé de préparation du dichlorure de l'acide chloro-2 éthanephosphonique
EP0071126B1 (fr) Procédé pour la préparation d'aldéhydes
DE2917620A1 (de) Verfahren zur herstellung von alkenen
DE19708722A1 (de) Verfahren zur Herstellung von Alkyl-1-alkoxyethylphosphinsäuren
EP0020988A2 (fr) Procédé pour préparer des esters alpha-cyano-benzyliques et intermédiaires à cet effet et leur préparation
DE3436478A1 (de) Verfahren zur herstellung von n,n-dimethyl-0-pyrimidinylcarbaminsaeureester
DE3035559A1 (de) Verfahren zur herstellung von diarylalkoxyphosphinen
DE2929636A1 (de) Verfahren zur herstellung von alkenen, neue alkene, deren verwendung und zwischenprodukte zu ihrer herstellung
DE3009242A1 (de) Verfahren zur herstellung von 3-(2,2-dichlor-vinyl)-2,2-dimethyl-cyclopropan-1-carbonsaeure-derivaten4
DE2929725A1 (de) Verfahren zur herstellung von 3-(2,2-dichlor-vinyl)-2,2-dimethylcyclopropan-1-carbonsaeureestern

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

17P Request for examination filed

Effective date: 19810306

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT NL

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT NL

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI NL

REF Corresponds to:

Ref document number: 3853

Country of ref document: AT

Date of ref document: 19830715

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3160455

Country of ref document: DE

Date of ref document: 19830728

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19840305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19840331

Ref country code: CH

Effective date: 19840331

Ref country code: BE

Effective date: 19840331

BERE Be: lapsed

Owner name: BAYER A.G.

Effective date: 19840305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19841001

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19841130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19841201

26N No opposition filed
REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881118